Epoxy-hexenylidene imines and insecticidal compositions thereof



Patented Sept. 4, 1951 EPOXY-HEXENYLIDENE IMINES AND INSEC- TICIDAL COMPOSITIONS THEREOF Richard R. Whetstone, Berkeley, Calif., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application August 16, 1947, Serial No. 769,065

16 Claims.

This invention relates to a new and highly useful class of heterocyclic aldimines; and to novel products formed by their autopolymerization and having the characteristics of dimers of the aldimines. The invention also includes a particularly advantageous method for the preparation of the products to which it relates.

The novel aldimines with which the invention is concerned contain an imino nitrogen atom that is attached by a double bond to a 3,4-dihydro-1,2-pyran-2-methylene radical, i. e., a 2,6-epoxy-5-hexenylidene radical and by a univalent bond to a hydrocarbon radical which may or may not be further substituted by one or more additional atoms or groups of atoms other than carbon and hydrogen. The 2,6-epoxy-5-hexenylidene radical may contain up to two lower alkyl groups, such as methyl, ethyl, and other alkyl gro ps containing up to about s x carbon atoms, attached to carbon atoms in the heterocyclic ring, or, more desirably, it may be the unsubstituted 2.6-epoxy-5-hexenylidene radical. A preferred group of the novel aldimines contains the unsubstituted 2.6-PpoXy- 5-hexenylidene radical and a total of from 9 to about 24 carbon atoms.

The aldimines of the present novel class have been found to po sess unexpected and particularly desirable properties. They are of notably improved value in numerous applications. Their value and their unexpected properties are due in part to the particular configuration relative to one another of the hydrocarbyl-substitutcd imino nitrogen atom, the oxygen atom in the 2,6-epoxy-5-hexenylldene radical, and the multiple bond in the heterocyclic ring of the 2,6- epoxy-S-hexenylidene radical. The unique structure of the present novel aldimines, including the character of the hydrocarbon group that is attached to the imino nitrogen atom, imparts characteristic and valuable properties that render the novel compounds distinctly different from aldimines heretofore known. By virtue of their unique structure, the new compounds are highly useful in many industrially and economically important applications in which previously known aldimines are unsuitable or much less desirable. Because of the low cost of the primary raw materials which may be employed for their manusubstantial advantages in the matter of low cost which further enhance their potential value in industry.

It has been discovered that the new aldimines may form by autopolymerization, i. e., by spontaneous polymerization, useful products having the characteristics of dimers of the aldimines. This tendency is most noticeable when the monomeric aldimine contains the unsubstituted 2,6-epoxy-5-hexenylidene radical, particularly when an aromatic hydrocarbon group is attached to the imino nitrogen atom. These products that are thus formed by autopolymerization of the novel monomeric aldimines have the same empirical formula, 1. e., contain the same proportions of elements, as the respective monomeric aldimines, but have in each case a molecular weight twice that of the monomeric aldimine. In the case of the lower aldimines that normally exist as liquids, the corresponding dimers frequently may be crystalline solids. Those aldimines which are normally solid, Or crystalline, may exhibit le s tendency to form the dimeric products. possibly because of a stabilizing effector the solid state vs. the liquid state. In any case, difference between the monomeric aldimine and its dimer. or between differentamixtures of the two, readily may be detected, for example by suitable determinations of melting point, solubility, molecular weight, or the like. The monomeric aldim ne and its dimer frequently ma coexist as an equilibrium mixture of the two, the position of the equilibrium depending upon the particular identity of the aldimine, and the conditions, such as temperature, etc., under which the mixture is maintained.

The chemical structure of these dimeric products is unknown. The dimers may revert tothe monomeric form, for example under the influence of heat, or of conditions liable to be encountered during chemical experimentation to determine their structure. Because of their complexity, and their susceptibility to the influences of their chemical environment, an elucidation of their exact chemical structure could require an exceedingly prolonged investigation, with uncertain liklihood of a completely successful outcome.

The novel compounds and products of the present invention, because of their'unique and especially advantageous properties, are useful for a variety of purposes. The aldimines may be hydrogenated to form valuable secondary amines containing the 2,6-epoxy-5-hexenylidene radical or its saturated analog, the 2,6-epoxyhexylidene radical, and alkyl substitution products thereof. The present aldimines and the dimers thereof, may be employed advantageously as active agents in the compounding and curing of rubber. They are highly useful chemical intermediates, e. g., as starting points for the synthesis of derived chemical products, such as products useful as lubricating oil additives, detergents. surfaceactive agents, biologically active compounds, and the like.

The present novel aldimines and the dimeric products formed by their autopolymerization are especially useful and valuable as insecticides. It has been found that the presence 01 the unsubstituted 2,6-epoxy-5-hexenylidene radical attached by a double bond to the imino nitro en atom, contributes significantly to the insecticidally activity of the aldimines and the dimers of such aldimines. For example, a mixture of N- phenyl-2,6-epoxy-5-hexenylidenimine with its dimer has been found to have a highly toxicaction towards insects, particularly housefiies, when applied in a manner and in amounts customarily employed in a standardized test for insecticidal activity. On the other hand, a dimethyl substitution product of this aldimine N-nhenyl-2,5-dimethyl-2,6-epoxy 5 hexenylidenimine, when tested in an equivalent manner, exhibited little if any toxic action upon houseflies ex osed to it in amounts within the range practicable for ordinary insecticidal usage.

I have discovered that the present novel aldimines may be prepared with particular advantags by reacting 2,6-epoxy-5-hexen-1-al, i. e., 3,4-dlhydro-1,2-pyran-2-carboxaldehyde 0 HC CHl Hg H-CHO or an alkyl substitution product thereof, e. g., one containing lower alkyl groups attached to the carbon atoms in the 2 and/or 5 positions of the heterccyclic ring, with a primary organic which would favor undesired side reactions, degradation, condensation, polymerization, or like reactions. The reaction most desirably-may be effected by reactlngthe stated reactants in the absence of any added materials having catalytic activity toward the reactants. The desired reaction may be brought about most efllcaciously by withdrawing the water formed in the reaction substantially as soon as it is formed. This may be accomplished in a variety of ways. One particularly effective method comprises heating a mixture of the selected reactants, in the presence of an organic solvent if desired, to the boiling point, and continuously separating water from the evolved vapors prior to their return, as

by reflux condensation, to the liquid reaction mixture. The separation of the water most conveniently may be accomplished by heating the reaction mixture in a reaction vessel equipped with a reflux distillation column having means for separating water from the vapors and/or the condensate. By maintaining a high total reflux, the water formed by the reaction may be removed substantially as soon as it is formed, the desired reaction thereby being favored and the reaction is for practical purposes complete. the reaction mixture remaining in the vessel may be treated in any suitable manner to recover the desired aldimine. If the desired aldimine is one that is autopolymerizable to a dlmeric product, e. g., one containing in its monomeric state the unsubstituted 2,6-epoxy-5-hexenylidene radical. appreciable amounts of the dlmeric product may be formed during the synthesis of the aldimine. The monomeric aldimine may be separated from its dimer at this time, or such separation may be postponed until any convenient later time, depending upon the method of recovery that is employed. The reaction mixture frequently may be submitted to fractional distillation to separate from the desired products any unreacted reactants that may be present. The monomeric aldimines also may be separated from their dimers by fractional distillation, although be,- cause of the lower volatility of the dimers it may be more desirable to effect their further purification by other means, such as by crystallization from organic solvents, by fractional precipitation with the aid of selective solvents, etc.

Although the foregoing procedure is widely applicable to the preparation of the novel products to which the invention is directed, suitable modifications therein may be made as desired or as required by the nature of the specific reactants that are employed. It thus may be desirable to include in the reaction-mixture a suitable inert solvent, i. e., an organic solvent that is inert both to the reactants and to the products of the reaction. Suitable solvents include, for example,

, amine in the absence of conditions or materials brought to completion within a reasonable and ethers, esters, hydrocarbons, heterocyclic oxygen-containing solvents, e. g., dioxane, and the like. By regulating the amount and the kind of The water, or the azeotropic mixture containing the water, may be separated from the total vapors evolved from the reaction mixture in any suitable manner, including fractional condensation, tolal condensation followed by stratification, extraction, salting out, treatment with drying agents, or the like.

The novel products to which the invention re-- lates may be prepared by either a continuous, an intermittent or batchwise type of process. Addition of the reactants may be made in one or a plurality of zones and the water formed by the reaction may be completely removed as it is formed, in one separating means, or a plurality of separating means may be employed with partial separation in each. If it is desired to prepare onl a single aldimine of the present class, only the requiredpair of reactants ordinarily will be employed. More than one aldimine may be prepared, if desired, by reacting a plurality of primary organic amines with one or a plurality of the above-described heterocyclic aldehydes. In the majority of cases, it is highly effective to heat the reaction mixture containing the heterocylic aldehyde and the primary organic amine to the boiling point, say, between 40 C. and 200 C.

under atmospheric pressures. If desired, pressures either above or below atmospheric may be employed to raise or lower, respectively, the boiling point from the temperature it would have under atmospheric pressures.

A variety of primary organic amines may be reacted with the above-described 2,6-epoxy-5- hexen-l-al and with its alkyl substitution products to obtain useful and valuable products according to the invention. Depending upon the particular primary organic amine that is employed, there may be obtained products having advantageous and distinctive characteristics above and beyond those characteristics imparted by the presence of the 2,6-epoxy-5-hexenylidene radical that is attached to the imino nitrogen atom. One group of particularly valuable aldimines which has been provided by the present invention contains the 2,6-epoxy-5-hexenylidene radical, or a lower-alkyl substitution product thereof, bonded to an imino nitrogen atom that is directly attached by a univalent bond to an aliphatic carbon atom that, in turn, is attached by a univalent bond to an oleflnic carbon atom. This olefinic carbon atom desirably may be attached to a terminal olefinic carbon atom i. e.. to a carbon atom of a methylene (=CH2) group. These N-(2-alkenyl) imines within the present class, because of the number and location of the multivalen". bonds, are highly reactive. They may be employed with advantage, for example, as ingredients of polymerizable, e. g., resinifiable, mixtures, and in other useful applications. Primary amines which may be employed for their preparation are exemplified by 2-propenyl amine (allyl amine), 2-methyl-2-propenyl amine (methallyl amine), 2-ethyl-2-propenyl amine, and the like and their homologs. A further valuable group of imines which has been provided by the present invention is represented by the imines in which the second group attached to the imino nitrogen atom is a higher alkyl group, preferably a straight-chain or branched-chain alkyl group containing from 8 to 18 carbon atoms, such as the octyl, nonyl. decyl, tetradecyl, hexadecyl, and octadecyl groups and their straight-chain and branched-chain homologs and branched-chain analogs. The novel aldimines within this group may be prepared conveniently according to the herein described method by reacting the corresponding primar alkyl amine containing from 8 to 18 carbon atoms with the heterocyclic aldehyde and removing the water that is formed substantially coincident with its formation, preferably as an azeotrope with a suitable inertyolatile organic solvent or a plurality of such solvents. Valuble N-aryl-2,6-epoxy-5-hexenylidenimines may be prepared by reacting 2,6-epxy- -hexen-1-al or one of its lower alkyl substitution products with primary aryl amines, such as aniline and its primary amine homologs and substibution products containing one or a plurality of aromatic rings. A preferred group of N-aryl- 2,6-epoxy-5-hexenylidenimines comprises those in which the 2,6-epoxy-5-hexenylidene radical is unsubstituted and the aryl group comprises not more than one aromatic nucleus- Functional groups in addition to the primary amino group may be present in the primary organic amine that is employed as the amine reactant, provided such additional groups and atoms are of such a. nature that they are non-reacting under the conditions of the process so as not to interfere with the successful execution of the process as by the formation of undesired 'by-products, etc.

The additional atoms may be present as in a heterocyclic ring, e. g., a nitrogen-, oxygen sulfur-containing or an analogous heterocyclic ring, or they may be present as substituents attached to carbon atoms in an open-chain or carbocyclic group of atoms. Representative substituent groups which ma be present include, for example, halogen, nitro, sulfo, esters, and like groups.

Further examples of specific primary organic amines which may be employed in the preparation of novel compounds within the invention, and in certain cases within the preferred groups of compounds hereinbefore and hereinafter referred to, include. amon others, the following: Z-butenyl amine, 3-pentenyl amine, 1-methy1-2- butenyl amine, 2-isopropyl-2-propenyl amine, 2- butyl-Z-propenyl amine, 2-phenyl-2-propenyl amine, 3-phenyl-2-propenyl amine, 2,4-hexadienyl amine, ethyl amine, propyl amine, isopropyl amine, pentyl amine, neo-pentyl amine, octyl amine, decyl amine, stearyl amine, oleyl amine. cyclohexyl amine, cyclopentyl amine, 3- cyclohexenyl amine, 2-methyl-3-cyclohexenyl amine, aniline, p-chloroaniline, the naphthyl amines, 3,5-xylidine, 2,4-xylidine, the nitroanilines, the nitroxylidines, 2,6-epoxy-5-hexenyl amine, 2,6-epoxyhexyl amine, N-methyl-2-piperidene amine, 2-aminopyridlne, 3-methyl-2- aminopyridine, furfuryl amine, tetrahydroi'urfuryl amine, and analogous and homologous primary amines.

The following example will illustrate the preparation of one of the compound to which the invention relates. In this and the following examples, the parts are by weight.

Example I Three hundred parts of 2,6-epoxy-5-hexen-1- al and 232 parts of aniline (equimolar quantities) were mixed in 325 parts of benzene with formation of heat and water. The water was removed as it was evolved by refluxing the mixture under a reflux column equipped with a phase separating head, heat being supplied as required, and withdrawing water until no more water was formed. When evolution of water was complete, the benzene was removed by distillation. The tarry reaction product wa extracted with 400 parts of 35 to 60 petroleum ether. There remained 81 parts of crude solid which after recrystallization from petroleum ether melted at 163 C. to 164 C. Distil ation of the petroleum ether extract resulted in the recovery of 144 parts of a viscous red oil distilling at -154 C. under 2 to 4 mm. Hg, and having a refractive index (n of 18025-15145.

The liquid product was identified as N-phenyl- 2,6-epoxy-5-hexenylidenimine having the probable structure It was found to contain 76.75% C, 7.07% H, and 8.94% N, and to have a molecular weight (ebullioscopic in benzene) of 198, compared to calculated values for the above formula of 76.98% C, 7.00% H, and 7.48% N, and a calculated molecular weight of 187. The solid crystalline product was identified as the dimer of the above imine. It was analyzed and found to contain 77.50%

7 C, 7.10% H, and 7.18% N, compared to the foregoing calculated values, and to have a molecular weight (ebuliioscopic in methyl ethyl ketone) of 373 compared to a theoretical value of 374. The liquid product in several weeks at room temperature darkened, became very viscous, and partly crystallized, the crystalline product being the same as the crystalline product directly prepared in the above experiment.

As illustrated in the foregoing example, it is convenient to employ the heterocyclic aldehyde and the primary organic amine in equimolar Example II A mixture of 112 'parts of 2,6-epoxy--hexenl-al, 75.5 parts of methallyl amine, and 130 parts of benzene was heated to boiling in a reaction vessel equipped with a reflux column with a phase separating head, and water was withdrawn until no more separated. About 3 hours heating was required. The remaining mixture was fractionally distilled under a pressure of 1 mm. Hg. After removal of the benzene, the following fractions were collected:

No. Distillation Temperature Amount Parts 1 55 to 57 C 5 2- 57to52C 71 '62 to 73 C 38 Bottoms 49 Fraction 2 was redistilled under a pressure of '5 mm. Hg with separation of 62 parts of N-methallyl 2,6 epoxy 5-hexenylidenimine distilling from 76.4 to 77.4 C. and having a refractive index m of 1.4828. The imine has a structure represented by the formula no on, on. t A t H HCH=NCH2 =CH:

Analyses: found, 72.17% C, 9.15% H, and 8.35%

N; calculated f0! C10H15ON, 72.72% C, 9.09% H,

and 8.48% N.

- Example III A mixture of 78.5 parts of 2,6-epoxy-5-hexen- 1-al, 96.5 parts of p-nitroaniline, and 200 parts of benzene was heated under reflux distillation and with withdrawal of evolved water until no more water separated. About 3 hours heating was required. After cooling, the benzene was decanted from the sparingly soluble product, and the product was dissolved in 200 parts of methyl ethyl ketone. The product was precipitated from solution by additionof 950 parts of isopropyl alcohol to the solution. The precipitate was dissolved in acetone and reprecipitated by addition of isopropyl alcohol to the acetone solution. Fifty-four parts of the recrystallized product were obtained. The product was a bright yellow solid melting at 214 to 217' 0.,

with decomposition, believed to be the dimer of \g the imine having the structure Hr no em 11c hn-cH=N.-Q No,

The solid was analyzed and found to contain 59.28% C, 5.76% H, and 11.1% N, compared to calculated value of 62.07% C, 5.21% H, and

Example IV crystallized from the cold reaction mixture in a yield of 43.5% based on the amounts of thereactants employed. After recrystallization from benzene, the product melted at 187' to 189 C. Analyses: Calculated for CzaHaNzOzOlz, 65.01% C, 5.46% H, 6.32% N, and 16.0% 01; found, 65.33% C, 5.46% H, 6.18% N, and 15.7% CL Example V A mixture of 224 parts of 2,6-epoxy-5-hexen l-al and 258 parts of n-octylamine in benzene was heated at the r'eflux temperature with withdrawal of water according to the method of the preceding examples until evolution of water ceased. The benzene was removed by distillation and the remaining residue was distilled under reduced pressure. N-octyl-2,6-epoxy-5- hexenylidenimine having the formula was recovered in a yield of 83% as the fraction distilling from 107 to 128 C. under a pressure of 1-2 mm.Hg, and having a refractive index (11,3 of 1.4681. Analyses: found, 74,81% 0, 11.20% H, and 6.07% N; calculated for CuHzsNO, 75.29% C. 11.28% H, and 6.27% N.

Example VI 2,6-epoxy-5-hexen-1-al and 2-aminopyridine I present in equimolar quantities were reacted in tion leaving a tarry residue.

benzene at the reflux temperature according to the method of the preceding examples, with withdrawal of water until evolution of water ceased, The benzene was removed by distilla- The residue was extracted with ethanol. The product, believed to be the dimer of N-(Z-pyridyl) -2,6-epoxy-5-' hexenylidenimine was recovered from the ethanol extract in a yield of 23%. The product was found to melt at 138-143 C., and it was found to have a molecular weight (ebullioscopic in benzene) of 373 compared to a molecular weight of 376 calculated for (Cnl-InONzh.

2,5-dimethyl-2,6-epoxy--hexen-1-al and aniline were reacted according to the method employed in the preceding examples. and the prod- CHi was recovered in a yield of 85% based on the amount of the reactants employed, as the fraction distilling between 110 C. and 114 C. under a pressure of 1 mm. Hg. Of this fraction, 90% distilled between 110 C. and 111 C. This lower boiling portion was found to have a refractive index (n of 1.5438. Analyses: Calculated for CiiHiiON: 78.60% C, 7.90% H, 6.51% N. Found 77.52% C, 7.87% H, 6.41% N.

Esample VIII 2,5-dimethyl-2,6-epoxy-5 hexen 1 al and methallyl amine were reacted according to the method of the preceding examples, and the product was recovered by fractional distillation. N- metha1iyl-2,5 dimethyl 2,6 epoxy-5-hexenylidenimine distilling at 64 to 65.5 C. under a pressure 01 1.5 millimeters Hg and having a refractive index (11 of 1.4740, was recovered in a yield of 88% of theory. Calculation for CmHioON: 74.61% C, 9.84% H, 7.25% N; found 74.39% C, 9.87% H, 7.03% N.

As I have indicated previously herein, the novel aldimines oi the present class which contain an unsubstituted 2,6-epoxy-5-hexenylidene radical attached to the imino nitrogen atom, and the dimeric products formed by their autopolymerization, particularly such lmines which also contain an aryl group directly attached to the imino nitrogen atom, and the corresponding dimeric products, have particular utility and value as insecticides, and ingredients of insecticidal compositions. Those imines, and their corresponding dimeric autopolymers, which contain a phenyl group or a substituted phenyl group attached to the imino nitrogen atom are particularly advantageous for this application. They may be applied either alone or in combination with other active or inactive substances, to plants, animals, fabrics, dwelling structures, and the like, by any suitable method, including spraying, dusting, dipping, etc., in the form of concentrated liquids, solutions, suspensions, emulsions, dusting powders, etc., or other suitable ways. For instance, they may be used advantageously in the form of dilute solutions in any of the solvents which are suited to use in insecticidal compositions and in which they are sufflciently soluble, including solvents such as petroleum distillates, paraflin oils, lignite tar oils, naphthenes, chlorinated hydrocarbons, chlorinated ethers, ketones,

10 monoand polyhydric alcohols. glycol ethers. 61 other solvents or mixtures thereof.

The above-mentioned new imines. and the dimeric products of their autopolymerization, are particularly valuable when it is desired to have an insecticidal agent having a strong lethal activity upon insects, as contrasted to these msecticides which exhibit a strong paralytic, but not always lethal action. Because of their highly lethal action, in conjunction with their low cost, the new insecticidal agents may be employed with advantage to supplement the action or less lethal agents which have a high paralytic action upon insects, with consequent economy at no sacrince in eiiectiveness.

For use in sprays, such, for example, as household insecticidal sprays and sprays to be used for control of insects, particularly flies, in other inhabited structures, the novel insecticides are valuable because they combine a high activity with a low volatility and a low odor and irritant action to man and other warm-blooded animals. They are useiul for application when it is desired to kill insects present at the time 01' application, and also as residual insecticides which are eiiective over a prolonged period of time alter the application. when used in this manner, the novel insecticides may be applied in the rorm of a dilute suspension in a non-odoriierous solvent medium, such as a highly reiined Kerosene distillate, either as the sole insecticidal agent or with other msecticioes. Relatively dilute solutions may be employed effectively, containing generally from about 042% to about 25% preieraoly irom about 2 to about 12% by weight of the active agent.

Insecticides provided by the invention have been used to kill adult housenies in a high proportion of those subjected at any one time to the action of the new insecticides. In one comparative test, employin the test method known as the Martinez Flowing Mist Test, groups of adult housefiies containing from 50 to individual flies in a cylindrical wire cage 5" in diameter and 8 in height were exposed under standardized conditions to a mist of an atomized solution of the insecticide being tested flowing through a horizontal tube 5 feet long and 14 inches in diameter, the cage being placed inside the tube near the outflow end. Under the conditions of the tests, and with the amounts of the compound being subjected to test, an equilibrium mixture of N-phenyl-2,6-epoxy-5-hexenylidenimine and its dimer caused the death of 46% of the houseflies exposed to its action. On the other hand, under equivalent conditions, N-phenyl-2,5-dimethyl- 2,6-epoxy-5-hexenylidenimine was found to be without lethal effects upon the housefiies exposed to its action. A comparison of the activity of a 1% solution of N-phenyl-5-hexenylidenirnine in acetone with a 2.5% solution of Lethane 384 Special (a commercial insecticide manufactured by the Rohm and Haas 00., Philadelphia, and containing a mixture of butyl carbitol thiocyahate and beta-thiocyano esters of higher fatty acids as the active ingredient) in odorless kerosene, showed the two solutions to be equivalent in lethal activity at the concentrations employed.

The novel insecticidal agents may be employed in the form of. emulsions, e. g., the compound or a solution of the compound in a suitable organic solvent, suitable organic solvents having been referred to above, may be emulsified in water with the aid of an emulsifying agent. such as sulphobated oil, a soap, a partial ester of a polyhydric alcohol, or the like, and the emulsion applied as by spraying upon plants, trees, and other things it is desired to protect-against the ravages of in-' sects. The novel compounds also may be applied in the form or dusts, mixed with or absorbed by or adsorbed upon suitable carriers, such as clay, talc, wood flour, sulfur, carbon black, or the like. The new compounds may be used as the sole insecticidal agent, or they may be used in conjunction with any of the heretofore known insecticides.

I claim as my invention: 1. N phenyI-iLB-epon hexenylidenimine having the structural formula 2. 2,6-epoxy 5 hexenylldenimine substituted 6. An imine wherein the imino nitrogen atom is attached by a double bond to a 2,6-epoxy-5- hexenylidene radical of the formula wherein R and R are radicals selected from the group consisting of hydrogen and alkyl radicals and by a single bond to a hydrocarbon radical.

'7. The dimer of an imine wherein the imino nitrogen atom is attached by a double bond to the 2,6-epoxy-5-hexenylidene radical and by a univalent bond to a hydrocarbon radical, said dimer being that product that forms by spontaneous polymerization of said lmine and having when purified the same empirical formula as said imineand a molecular weight substantially twice that of said imine.

8. An insecticidal composition comprising at least one material of the group consisting of N- phenyl-2,6-epoxy-5-hexenylidenimine and the dimer thereof, and a carrier therefor, said dimer being that normally solid product that forms spontaneously when said N-phenyl-2.6-epoxy-5- hexenylidenimine is allowed to stand at about said dimer being that normally solid product that forms spontaneously when said N-phenyl-2,6-

* epoxy-S-hexenylidenimine is allowed to stand at room temperature, and having when purified a I about room temperature, and having when purlfled a melting point of substantially 163 C. to 164 C., the same empirical formula as said N- phenyl-2,6-epoxy 5 hexenylldenimine and a molecular weight substantially twice that of said N-phenyl-2,6-epoxy-5-hexenylidenimine.

10. The method of preparing an N-hydrocarbyl-2,6-epoxy 5 hexenylidenimine which comprises heating 2,6-epoxy 5 -hexen-1-al, having the structural formula 3 Jan-c H AER-CHO in the presence of an inert volatile organic solvent, removing water from the mixture substantially as it is formed, and recovering from the mixture an N-aryl-2,6-epoxy-5-hexenylidenimine having the structural formula IIF CH:

H llH-CH=N-aryl 12. The method of preparing an N-hydrocarbyl-2,6-epoxy-5-hexenylidenimine which comprises reacting a 2,6-epoxy-5-hexen-1-al containing from no substituent groups up to two alkyl nuclear substituent groups with an N-hydrocarbyl primary organic amine, separating from the reactants water formed by the reaction substantiallycoincident with its formation, and I recovering an N-hydrocarbyl-2,6-epoxy-5-hexenylidenimine wherein the 2,6-epoxy-5 -hexenylidene radical contains from no substituent groups up to two alkyl nuclear substituent groups.

13. An imine wherein the imino nitrogen atom is attached by a double bond to the 2.6-epoxy- -hexenylidene radical, said 2,6-epoxy-5-hexenylidene radical having the structural formula and by a univalent bond to an aryl group.

14. An insecticidal composition comprising at least one material of the group consisting of (a) an imine wherein the imino nitrogen atom is attached by a double bond to the 2,6-epoxy-5-hexenyiidene radical said radical having the struc-' tural formula C 110 cm terial of-the group consisting of (a) an N-aryi- 2,6-epoxy-5-hexenylidenimine and (b) the dimer of said imine, and a carrier therefor, said dimer being that product that forms by spontaneous f4 polymerization of said imine and having when purified the same empirical formula as said imine and a molecular weight substantially twice that of said imine. v

16. N-phenyi-2.6-epoxy 5 hexenylidenimine having the structural formula cn-cn=N-c.m

, O I and the dimer of said N-phenyl-2,8-epoxy-5- hexenylidenimine, said dimer being that normally solid product that forms spontaneously when said N-phenyl-ZQ-epoxy 5 hexenylidenimine is allowed to stand at about room' temperature, and having when purified a melting point of substantially 163 0. to 184 0., the same empirical formula as said N-phenyl-ZG-epogy-S-hexenylidenimine and a moleeular'weight'substantially twice that of said N-phenyI-iLG- D Y-S-hexenylidenimine.

RICHARD R. WHE'I'S'IONE.

REFERENCES man The following references are of record in the file of this patent:

UNITED STATES PATENTS Lal orge June 3, 1947 OTHER REFERENCES Jacques, Chemical Abstracts. vol. 40, 1948, 988% 3749-8760. 

14. AN INSECTICIDAL COMPOSITION COMPRISING AT LEAST ONE MATERIAL OF THE GROUP CONSISTING OF (A) AN IMINE WHEREIN THE IMINO NITROGEN ATOM IS ATTACHED BY A DOUBLE BOND TO THE 2,6-EPOXY-5-HEXENYLIDENE RADICAL SAID RADICAL HAVING THE STRUCTURAL FORMULA 